EP1373226B1 - Process for the enhancement of cycle life of a zinc-chromium based catalyst in the synthesis of 2-methylpyrazine - Google Patents

Process for the enhancement of cycle life of a zinc-chromium based catalyst in the synthesis of 2-methylpyrazine Download PDF

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Publication number
EP1373226B1
EP1373226B1 EP01934298A EP01934298A EP1373226B1 EP 1373226 B1 EP1373226 B1 EP 1373226B1 EP 01934298 A EP01934298 A EP 01934298A EP 01934298 A EP01934298 A EP 01934298A EP 1373226 B1 EP1373226 B1 EP 1373226B1
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Prior art keywords
catalyst
temperature
methylpyrazine
hours
zinc
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EP01934298A
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German (de)
English (en)
French (fr)
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EP1373226A1 (en
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Sai Prasad Potharaju Seetharamanjaneya
Kondapuram Vijaya Raghavan
Panja Kanta Rao
Shivanand Janardan Kulkarni
Katabathini Narasimha Rao
Rajesh Gapinath
Suresh Farsinavis
Harshadas Mitaram Meshram
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Council of Scientific and Industrial Research CSIR
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Council of Scientific and Industrial Research CSIR
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for the enhancement of the cycle life of zinc chromium based catalyst in the synthesis of 2-methylpyrazine. More particularly, the present invention relates to an improved process for the enhancement of the cycle-life of the catalyst used in the synthesis of 2-methylpyrazine.
  • 2-methylpyrazine is used as an intermediate in the production of pyrazinamide, an anti-tubercular drug. It is known to react ethylenediamine and propyleneglycol on a zinc-based catalyst by a vapour phase process to produce 2-methylpyrazine. 2-methylpyrazine, in turn, is converted to 2-cyanopyrazine by catalytic ammoxidation of 2-methylpyrazine using ammonia and oxygen or air. In the last step, 2-cyanopyrazine is hydrolyzed to 2-amidopyrazine, which is popularly called as pyrazinamide.
  • the duration of time when the catalyst exhibits continuous steady-state activity/selectivity before it starts showing unacceptable activity and selectivity and requires regeneration is normally defined as its cycle-life. After regeneration, the catalyst regains its activity/selectivity either fully or partially and is used for the next cycle. After a few regenerations, the catalyst gets deactivated by exhibiting unacceptable activity/selectivity or both even after regeneration and needs to be replaced with a fresh catalyst.
  • the total time for which the catalyst is put into operation before discharge is called the total life or simply the life of the catalyst. Longer cycle-life and thus longer catalyst life are preferred for catalysts operating in fixed bed reactors. The commercial process becomes economical when the catalyst not only offers high activity and high selectivity towards the required product but also possesses sufficient cycle-life and thus, the total life.
  • the drawbacks of the prior art are as follows:
  • the catalyst referred to above in item (i) has a poor cycle life, though the 2-methylpyrazine yields are promising.
  • Zinc based catalysts promoted with Ce, Mg etc. though offer high initial activity, their life times are of the order of 25 hours.
  • Catalyst reported by Forni et al, cited in item (ii) above, has the first cycle life of about 150 hours. Subsequent second and third cycle lives after regenerations were lower compared to the first cycle. The total catalyst life after three regenerations (with the catalyst giving a maximum of 50% conversion), was reported to be 450 hours.
  • Non-metallic sulphate or bisulphate promoted zinc-based catalysts reported in item (iv) referred above also were reported to be tested for 144 hours with acceptable conversions and yields. Thus, the catalysts reported in the prior art possess their cycle lives less than 150 hours.
  • the main object of the present invention is to provide a process for the enhancement of the cycle-life of the catalyst used in the synthesis of 2-methylpyrazine from ethylenediamine and propyleneglycol by a vapour phase catalytic process which obviates the drawbacks as detailed above.
  • Another object of the present invention is to provide the operating conditions wherein the conversions with respect to ethylenediamine and propyleneglycol are in the order of 100%.
  • Yet another object of this invention is to provide the operating conditions wherein the yield of 2-methylpyrazine is obtained in the range of 70-80%.
  • Yet another object of the present invention is to provide the operating conditions wherein the product of the reaction contains pyrazine as the main byproduct and its composition in the product is less than 10-12%.
  • Still another object of this invention is to provide a method for the regeneration of the catalyst after first cycle life such that the regenerated catalyst again gives ethylenediamine and propyleneglycol conversions and 2-methylpyrazine and pyrazine selectivities similar to those obtained on the fresh catalyst.
  • the present invention provides a process for the synthesis of 2-methylpyrazine, said process comprising reacting ethylenediamine and propyleneglycol at a molar ratio of 1 - 1.5:1 in a fixed bed reactor over a zinc-chromium based catalyst at a temperature in the range of 300 - 409°C, characterised in that an enhancement in cycle life of the zinc-chromium based catalyst is obtained by increasing the temperature of the reaction step-wise dependent on the conversion of the reactant stream to the product stream,with the temperature being increased when the level of pyrazine in the product mixture reaches a maximum level of 10-12%, from an initial temperature of 300 to 350°C until either a final temperature of 380 to 409°C is reached or the level of pyrazine exceeds the maximum level, and in that the weight hourly spaced velocity (WHSV) is 0.15 - 1.00 per hour.
  • WHSV weight hourly spaced velocity
  • the step-wise temperature increase is carried out starting at temperatures in the range 300 - 340°C dependent on the conversion rate of the reactant stream.
  • the conversion of ethylenediamine and propyleneglycol is about 100%.
  • the yield of 2-methylpyrazine is in the range of 70 - 80% and pyrazine levels in the range of 2 - 12%.
  • the catalyst after use is subject to at least one regeneration, said regeneration comprising washing the used catalyst in steam, calcining in air at 400°C till no carbon dioxide is observed in the effluent and reducing in hydrogen at 400°C for 4 hours.
  • the cycle life of the catalyst can be enhanced to 500 hours before regeneration.
  • the catalyst after the first regeneration give another cycle life of 500 hours and after the second regeneration gives yet another cycle life of 500 hours and is found to be still active.
  • Zinc-chromium catalysts are prepared using the commercial Zn-Cr catalyst (Engelhard-0312 T) as the base material. Aqueous solution of palladium sulphate is impregnated on the base material such that the composition of the palladium sulphate is in the range of 0.5 - 5.0% by weight, preferentially in the range of 1 - 3%. The impregnated catalyst is subjected to drying in air at a temperature in the range of 100 - 150°C.
  • the catalyst can be used advantageously in the process for the production of 2-methylpyrazine from ethylenediamine and propyleneglycol.
  • the catalyst prepared by the procedure described herein was loaded into a fixed bed reactor and preheated with a gas mixture of hydrogen and nitrogen or hydrogen alone, at a temperature of 300 - 500°C, preferentially in the range of 300 - 400°C, for a period of 4 - 8 hours.
  • the feed to the reactor can be made by mixing aqueous solutions of ethylenediamine and propyleneglycol in the molar ratio of 3:1, preferentially in the ratio 2:1 and more preferentially 1.2:1.
  • the water content in the feed mixture is 30-80% by volume.
  • the water content can be reduced to 30-60% by volume.
  • Pure nitrogen is optionally fed into the reactor.
  • the liquid feed is vaporized in a preheater and passed into the reactor at a weight hourly space velocity (WHSV) of 0.25 - 1.00 per hour or preferentially in the range of 0.25 - 0.75 per hour.
  • WHSV weight hourly space velocity
  • the catalyst bed is initially maintained at a temperature of 300 - 350°C and the reaction is carried out.
  • the product is collected by cooling the condensables and analyzing them on a gas chromatograph.
  • the reaction is continued at the same temperature as long as the yield of 2-methylpyrazine and the main by-product, pyrazine levels are in the acceptable limits.
  • the reaction temperature is raised by 10 - 50°C and more preferentially in the range of 10 - 30°C.
  • the procedure described above is continued until the reactor temperature reaches 380 - 409°C or the pyrazine levels exceed beyond the set limit.
  • the catalyst can be regenerated even after working for 500 hours and exhibiting a tendency of reduction in the yields of 2-methylpyrazine or increase in pyrazine levels beyond the acceptable levels.
  • the regeneration procedure involves treating the catalyst first at 400 - 500°C in nitrogen, preferentially in steam for 4 - 6 hours, then oxidizing in air or preferentially in a mixture of oxygen and nitrogen at 400°C for 4 - 6 hours and finally reducing the catalyst in a mixture of hydrogen and nitrogen or hydrogen alone at 300 - 350°C, preferentially at 300 - 400°C for 4 - 6 hours.
  • the catalyst activity is restored after regeneration.
  • the catalyst, after the first regeneration is subjected to the reaction temperature again starting at lower temperatures in the range of 300 - 350°C, preferentially in the range of 310 - 340°C and following the same procedure as described in the evaluation of the fresh catalyst. It is observed that the regenerated catalyst is active and selective for the next 500 hours of operation as illustrated in Figure 2.
  • the catalyst after the second regeneration is also found to be active and selective for the next 500 hours of operation as illustrated in Figure 4.
  • the combined life of the catalyst after the first regeneration itself is 1000 hours and after the second regeneration the life of the catalyst is 1500 hours.
  • the total life of the catalyst is only 1500 hours. Further regeneration and reactions could enhance the life by several folds. This is an important aspect of the invention since the total life of the best catalyst reported in literature, so far, is of the order of 430 hours, that too, after three regenerations and allowing the conversion to fall to about 50%.
  • Example 1 150 grams of another fraction of the fresh catalyst, as used in Example 1, was loaded into the reactor and the same activation procedure was carried out as described in Example 1. After reduction at 400°C for 4 hours the catalyst was cooled to the reaction temperature of 320°C in nitrogen flow and the reaction continued with the liquid feed. The performance of the catalyst was monitored every hour. As long as the yield of 2-methylpyrazine was in the rante of 70 - 80% and the pyrazine levels in the reaction effluent was below 10 - 12%, the reaction was continued. As the pyrazine level crossed beyond the set value, the reaction temperature was increased in steps and the procedure continued. The performance of the catalyst is depicted in Figure 1.
  • the reaction was stopped for regenerating the catalyst.
  • the catalyst was first treated in steam at 400°C for 4 hours, calcined in air at the same temperature till the reactor effluent showed no indication of carbon dioxide formation and then it was reduced at the same temperature in hydrogen for 4 hours.
  • the reaction was continued again at 320°C following the stepwise temperature increasing policy.
  • the performance of the regenerated catalyst is depicted in Figure 2. The catalyst exceeds 500 hours of operation even at 380°C with required performance parameters giving further scope of increased cycle life.
  • the reaction was stopped for the second regeneration.
  • the catalyst was first treated in steam at 400°C for 4 hours, calcined in air at the same temperature till the reactor effluent showed no indication of carbon dioxide formation and then it was reduced at the same temperature in hydrogen for 4 hours.
  • the reaction was continued again at 320°C following stepwise increase in temperature.
  • the performance of the second time regenerated catalyst is depicted in Figure 4. The catalyst gave another 500 hours of operation with the required performance parameters giving further scope for increased cycle life.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP01934298A 2001-03-30 2001-03-30 Process for the enhancement of cycle life of a zinc-chromium based catalyst in the synthesis of 2-methylpyrazine Expired - Lifetime EP1373226B1 (en)

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Application Number Priority Date Filing Date Title
PCT/IN2001/000069 WO2002079171A1 (en) 2001-03-30 2001-03-30 Process for the enhancement of cycle life of a zink-chromium based catalyst

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EP1373226A1 EP1373226A1 (en) 2004-01-02
EP1373226B1 true EP1373226B1 (en) 2007-07-04

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EP (1) EP1373226B1 (zh)
JP (1) JP2004533913A (zh)
KR (1) KR100620789B1 (zh)
CN (1) CN1233632C (zh)
AT (1) ATE366243T1 (zh)
DE (1) DE60129255D1 (zh)
WO (1) WO2002079171A1 (zh)

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CN103691443A (zh) * 2013-12-13 2014-04-02 广西大学 一种用于合成2，5-二甲基吡嗪的催化剂及其制备方法

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IT1196480B (it) * 1986-07-08 1988-11-16 Bracco Ind Chimica Spa Processo per la preparazione di composti eterociclici azotati

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JP2004533913A (ja) 2004-11-11
KR20040004570A (ko) 2004-01-13
ATE366243T1 (de) 2007-07-15
DE60129255D1 (de) 2007-08-16
CN1494533A (zh) 2004-05-05
WO2002079171A1 (en) 2002-10-10
CN1233632C (zh) 2005-12-28
KR100620789B1 (ko) 2006-09-13
EP1373226A1 (en) 2004-01-02

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